EP2982713A1 - Verbesserte Polyester-Ether-Harzmischungen - Google Patents

Verbesserte Polyester-Ether-Harzmischungen Download PDF

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Publication number
EP2982713A1
EP2982713A1 EP14179890.0A EP14179890A EP2982713A1 EP 2982713 A1 EP2982713 A1 EP 2982713A1 EP 14179890 A EP14179890 A EP 14179890A EP 2982713 A1 EP2982713 A1 EP 2982713A1
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EP
European Patent Office
Prior art keywords
magnesium
transition metal
weight
composition
masterbatch
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EP14179890.0A
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English (en)
French (fr)
Inventor
Eva-Maria LEUSCHNER
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Trevira Holdings GmbH
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INVISTA TECHNOLOGIES SÀRL
Invista Technologies SARL Switzerland
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Application filed by INVISTA TECHNOLOGIES SÀRL, Invista Technologies SARL Switzerland filed Critical INVISTA TECHNOLOGIES SÀRL
Priority to EP14179890.0A priority Critical patent/EP2982713A1/de
Priority to US15/506,547 priority patent/US10428199B2/en
Priority to PCT/US2015/043595 priority patent/WO2016022550A1/en
Priority to CN201580053387.XA priority patent/CN107075136B/zh
Publication of EP2982713A1 publication Critical patent/EP2982713A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to novel polyester-ether containing polyester resins. Articles, preforms and containers comprising these resins show improved oxygen barrier properties.
  • the present invention also relates to masterbatches for use in preparing said polyester-ether containing polyester resins.
  • Polyesters have been replacing glass and metal packaging materials due to their lighter weight, decreased breakage compared to glass, and potentially lower cost.
  • Organic oxygen scavenging materials have been developed partly in response to the food industry's goal of having longer shelf-life for packaged food. These oxygen scavenging materials are incorporated into at least a portion of the package and remove oxygen from the enclosed package volume which surrounds the product or which may leak into the package, thereby inhibiting spoilage and prolonging freshness.
  • Suitable oxygen scavenging materials include oxidizable organic polymers which may react with ingressing oxygen.
  • an oxidizable organic polymer is a polyether.
  • the polyether is typically used as a polyester-ether copolymer and in low amounts of less than 10 weight percent of the packaging material.
  • the polyester-ether is dispersed in the matrix polyester phase and interacts with a suitable oxygen scavenging catalyst that catalyzes the reaction of the ingressing oxygen with the polyether.
  • Oxygen scavenging catalysts are typically transition metal compounds, for example an organic or inorganic salt of cobalt. Other examples include manganese, copper, chromium, zinc, iron and nickel.
  • Polyester containers comprising polyester-ethers and an oxygen scavenging catalyst show excellent oxygen barrier properties.
  • the transition metal based oxygen scavenging catalyst may impart color to the resin and may catalyze unwanted degradation processes in the resin. Therefore, it is often desirable to minimize the amount of metal based oxygen scavenging catalysts.
  • the introduction of a magnesium compound into the polyether-containing polymer resin improves oxygen barrier properties if the resin further comprises a traditional transition metal-based oxidation catalyst such as a cobalt compound.
  • a traditional transition metal-based oxidation catalyst such as a cobalt compound.
  • the magnesium compound acts as a co-catalyst in combination with the transition metal-based oxidation catalyst and that both compounds work together in a complementary manner to surprisingly improve oxygen barrier properties of the resin.
  • already a very small amount of the magnesium compound provides a very substantial improvement in oxygen barrier properties.
  • the overall amount of transition metals in the resin can be reduced. Given the diagonal relationship between magnesium and lithium in the periodic table of elements (PSE), the same advantages can be expected for the corresponding compositions in which magnesium is replaced with lithium.
  • composition for preparing articles, preforms or containers comprising:
  • a masterbatch for use in blow-molding polyester articles comprising:
  • a "salt-and-pepper" mixture of masterbatches more specifically a kit-of-parts for use in preparing articles, preforms or containers comprising two masterbatches which may optionally be in admixture:
  • articles, preforms or containers prepared from a composition, masterbatch or kit-of-parts according to the above-mentioned aspects.
  • polyesters suitable for the present invention can be prepared by one of two processes, namely: (1) the ester process and (2) the acid process.
  • the ester process is where a dicarboxylic ester (such as dimethyl terephthalate) is reacted with ethylene glycol or other diol in an ester interchange reaction.
  • Catalysts for use in the ester interchange reaction are well known and may be selected from manganese, zinc, cobalt, titanium, calcium, magnesium or lithium compounds. Because the reaction is reversible, it is generally necessary to remove the alcohol (e.g. methanol when dimethyl terephthalate is employed) to completely convert the raw materials into monomers.
  • the catalytic activity of the interchange reaction catalyst may optionally be sequestered by introducing a phosphorus compound, for example polyphosphoric acid, at the end of the ester interchange reaction. Then the monomer undergoes polycondensation.
  • the catalyst employed in this reaction is typically an antimony, germanium, aluminum, zinc, tin or titanium compound, or a mixture of these. In some embodiments, it may be advantageous to use a titanium compound.
  • an acid such as terephthalic acid
  • a diol such as ethylene glycol
  • the direct esterification step does not require a catalyst.
  • the monomer then undergoes polycondensation to form polyester just as in the ester process, and the catalyst and conditions employed are generally the same as those for the ester process.
  • the ester process there are two steps, namely: (1) an ester interchange, and (2) polycondensation.
  • the acid process there are also two steps, namely: (1) direct esterification, and (2) polycondensation.
  • Suitable polyesters can be aromatic or aliphatic polyesters, and are preferably selected from aromatic polyesters.
  • An aromatic polyester is preferably derived from one or more diol(s) and one or more aromatic dicarboxylic acid(s).
  • the aromatic dicarboxylic acid includes, for example, terephthalic acid, isophthalic acid, 1,4-, 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid and 4,4'-diphenyldicarboxylic acid (and of these terephthalic acid is preferred).
  • the diol is preferably selected from aliphatic and cycloaliphatic diol(s), including, for example, ethylene glycol, 1,4-butanediol, 1,4-cyclohexane dimethanol, and 1,6-hexanediol (and of these, aliphatic diols, and preferably ethylene glycol, is preferred).
  • Preferred polyesters are polyethylene terephthalate (PET) and polyethylene-2,6-naphthalene dicarboxylate (also referred to herein as polyethylene-2,6-naphthalate), and particularly preferred is PET.
  • polyesters include those produced from the reaction of a diacid or diester component comprising at least 65 mol.-% aromatic diacid (preferably terephthalic acid) or the C 1 -C 4 dialkyl ester of the aromatic acid (preferably C 1 -C 4 dialkylterephthalate), for example at least 70 mol.-% or at least 75 mol.-% or at least 95 mol.-%, with a diol component comprising at least 65 mol.-% diol (preferably ethylene glycol), for example at least 70 mol.-% or at least 75 mol- % or at least 95 mol.-%.
  • a diacid or diester component comprising at least 65 mol.-% aromatic diacid (preferably terephthalic acid) or the C 1 -C 4 dialkyl ester of the aromatic acid (preferably C 1 -C 4 dialkylterephthalate), for example at least 70 mol.-% or at least 75 mol.-% or at least 95 mol.-%
  • Exemplary polyesters include those wherein the diacid component is terephthalic acid and the diol component is ethylene glycol, thereby forming polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the polyester may be modified by one or more diol components other than ethylene glycol.
  • the polyester is a copolyester.
  • Suitable diol components of the described polyester may be selected from 1,4-cyclohexane-dimethanol, 1,2-propanediol, 1,4-butanediol, 2,2-dimethyl-1, 3-propanediol, 2-methyl-1,3-propanediol (2MPDO) 1,6-hexanediol, 1,2-cyclo-hexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and diols containing one or more oxygen atoms in the chain, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or mixtures of these, and the like.
  • these diols contain 2 to 18, preferably 2 to 8 carbon atoms.
  • Cycloaliphatic diols can be employed in their cis- or trans-configuration or as mixture of both forms.
  • Suitable modifying diol components can be 1,4-cyclohexanedimethanol or diethylene glycol, or a mixture of these.
  • the polyester may be modified by one or more acid components other than terephthalic acid.
  • the polyester is a copolyester.
  • Suitable acid components (aliphatic, alicyclic, or aromatic dicarboxylic acids) of the linear polyester may be selected, for example, from isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, bibenzoic acid, or mixtures of these and the like.
  • Typical functional acid derivatives include the dimethyl, diethyl, or dipropyl ester of the dicarboxylic acid or its anhydride.
  • the polyester is a copolyester of ethylene glycol with a combination of terephthalic acid and isophthalic acid and/or 5-sulfoisophthalic acid.
  • the isophthalic acid can be present from about 0.05 mol.-% to about 10 mol.-% and the 5-sulfoisophthalic acid from can be present from about 0.1 mol.-% to about 3 mol.-% of the copolymer.
  • the polyester is selected from polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, copolymers of polyethylene terephthalate, copolymers of polyethylene naphthalate, copolymers of polyethylene isophthalate, or mixtures thereof; for example the polyester can be a copolymer of polyethylene terephthalate, such as poly(ethylene terephthalate-co-ethylene isophthalate) or poly(ethylene terephthalate-co-ethylene 5-sulfoisophthalate).
  • composition for preparing an article, preform or container comprises 80-99.5 parts by weight of a polyester, including 85-99.5, 90-99.5, or 95-99.5 parts by weight of the polyester.
  • the composition comprises 90-99.5 parts by weight of the polyester.
  • copolyester-ethers suitable for the present invention comprise one or more polyester segments and one or more polyether segments.
  • the polyether segments advantageously have a number-average molecular weight of from about 200 to about 5000 g/mol.
  • the polyether segments of the copolyester-ether has a number-average molecular weight of from about 600 to about 2500 g/mol, more specifically between about 800 to about 1800 g/mol or between about 1000 to about 1600 g/mol.
  • the one or more polyether segments may be present in an amount of about 5 to about 95 wt.-% of the copolyester-ether.
  • the polyether segments are present in an amount of about 5 to about 49 wt.-%, more specifically about 10 to about 40 wt.-%, or in particular about 25 to about 45 wt.-% or about 25 to about 40 wt.-%, in all cases based on the copolyester-ether.
  • copolyester-ethers suitable for the present invention comprise one or more polyether segments in amounts so that the weight ratio of the one or more polyether segments to the total amount of base polyester and polyester segments in the composition is about 0.2 to about 10 wt.-%, more specifically about 0.5 to about 10 wt.-%, or in particular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.
  • the polyether segment is a poly (C 2 -C 6 -alkylene glycol) segment.
  • the C 2 -C 6 -alkylene glycol may be a linear or branched aliphatic C 2 -C 6 -moiety.
  • copolyester-ethers include poly(ethylene glycol), linear or branched poly(propylene glycol), linear or branched poly(butylene glycol), linear or branched poly(pentylene glycol), linear or branched poly(hexylene glycol) as well as mixed poly (C 2 -C 6 -alkylene glycols) obtained from two or more of the glycolic monomers used in preparing the before-mentioned examples.
  • the polyether segment is a linear or branched poly(propylene glycol) or a linear or branched poly(butylene glycol).
  • the copolyester-ethers suitable for the present invention also comprise one or more polyester segments.
  • the type of polyester in these segments is not particularly limited and can be any of the above-referenced polyesters.
  • the copolyester-ether comprises a polyethylene terephthalate (co)polymer segment.
  • the copolyester-ether comprises a polyethylene terephthalate (co)polymer segment and a linear or branched poly(butylene glycol) segment.
  • the copolyester-ether can be produced by ester interchange with the dialkyl ester of a dicarboxylic acid.
  • dialkyl esters of dicarboxylic acids undergo transesterification with one or more glycols in the presence of a catalyst such as zinc acetate as described in WO 2010/096459 A2 , incorporated herein by reference.
  • a suitable amount of elemental zinc in the copolyester-ether can be about 35 to about 100 ppm, for example about 40 to about 80 ppm, by weight of the copolyester-ether.
  • the poly(alkylene oxide) glycols replace part of these glycols in these transesterification processes.
  • the poly(alkylene oxide) glycols can be added with the starting raw materials or added after transesterification.
  • the monomer and oligomer mixture can be produced continuously in a series of one or more reactors operating at elevated temperature and pressures at one atmosphere or lesser.
  • the monomer and oligomer mixture can be produced in one or more batch reactors. Suitable conditions for these reactions are temperatures of from about 180°C to 250°C and pressures of from about 1 bar to 4 bar.
  • the mixture of copolyester-ether monomer and oligomers undergoes melt-phase polycondensation to produce a polymer.
  • the polymer is produced in a series of one or more reactors operating at elevated temperatures. To facilitate removal of excess glycols, water, and other reaction products, the polycondensation reactors are run under a vacuum.
  • Catalysts for the polycondensation reaction include compounds of antimony, germanium, tin, titanium and/or aluminum. In some embodiments, it may be advantageous to use an titanium compound.
  • a suitable amount of elemental Ti can be about 5 to about 50 ppm, for example about 10 to 30 ppm.
  • Reaction conditions for polycondensation can include (i) a temperature less than about 290°C, or about 10°C higher than the melting point of the copolyester-ether; and (ii) a pressure of less than about 0.01 bar, decreasing as polymerization proceeds.
  • This copolyester-ether can be produced continuously in a series of one or more reactors operating at elevated temperature and pressures less than one atmosphere. Alternatively this copolyester-ether can be produced in one or more batch reactors.
  • the intrinsic viscosity after melt phase polymerization can be in the range of about 0.5 dl/g to about 1.5 dl/g.
  • Antioxidants and other additives can be added before and/or during polymerization to control the degradation of the polyester-ether segments.
  • the copolyester-ethers can be produced by reactive extrusion of the polyether with the polyester.
  • the polyether does not fully react with the polyester but is partly present as an intimate blend of the polyester and polyether. Therefore, throughout the specification and claims, the reference to a copolyester-ether comprising one or more polyester segments and one or more polyether segments is to be understood as referring to the respective copolyester-ethers, blends of respective polyesters and polyethers, and mixtures comprising both the respective copolyester-ethers and blends of the respective polyesters and polyethers.
  • the copolyester-ether is preferably used in amounts of about 0.5 to about 20 wt.-% in relation to the final composition.
  • the amount of the copolyester-ether is selected within the range of about 0.5 to about 20 wt.-%, in relation to the final container, preform or article composition, so that the amount of polyether segments to the total amount of base polyester and polyester segments in the composition is about 0.2 to about 10 wt.-%, more specifically about 0.5 to about 10 wt.-%, or in particular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-% or about 1 to about 2.5 wt.-%.
  • the copolyester-ether contains one or more polyether segments in an amount of about 5 to about 49 wt.-%, in particular about 15 to about 45 wt.-%, more specifically about 20 to about 40 wt.-%, and that the amount of the copolyester-ether is selected so that the amount of polyether segments to the total amount of base polyester and polyester segments in the composition is about 0.5 to about 10 wt.-% , in particular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.%.
  • the polyether segments in the copolyester-ether have a number-average molecular weight of from about 600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol, that the copolyester-ether contains one or more polyether segments in an amount of about 15 to about 45 wt.-%, in particular about 20 to about 40 wt.-%, and that the amount of the copolyester-ether is selected within the range of about 0.5 to about 20 wt.-%, in relation to the final composition, so that the amount of polyether segments to the total amount of base polyester and polyester segments in the composition is about 0.5 to about 10 wt.-%, in particular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.
  • the polyether segments in the copolyester-ether are selected from a linear or branched poly(propylene glycol) or a linear or branched poly(butylene glycol) having a number-average molecular weight of from about 600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol, that the copolyester-ether contains one or more polyether segments in an amount of about 15 to about 45 wt.-%, in particular about 20 to about 40 wt.-%, and that the amount of the copolyester-ether is selected within the range of about 0.5 to about 20 wt.-%, in relation to the final composition, so that the amount of polyether segments to the total amount of base polyester and polyester segments in the composition is about 0.5 to about 10 wt.-% , in particular about 0.7 to about 5 wt.-%, or about 0.5 to about 1.5 wt.-%, or about 1 to about 2.5 wt.-%.
  • the polyester is produced using an antimony-based polycondensation catalyst.
  • the compositions contain about 50 to about 500 ppm antimony. This is a typical range for compositions prepared using antimony-based polyester base resins.
  • compositions, kit-of-parts and processes of the invention further utilize a transition metal-based oxidation catalyst selected from a cobalt, manganese, copper, chromium, zinc, iron, or nickel compound.
  • a transition metal-based oxidation catalyst selected from a cobalt, manganese, copper, chromium, zinc, iron, or nickel compound.
  • the transition metal-based oxidation catalyst may be present in the form of a metal salt.
  • suitable counter ions for the transition metal include, but are not limited to, carboxylates, such as neodecanoates, octanoates, stearates, acetates, naphthalates, lactates, maleates, acetylacetonates, linoleates, oleates, palminates or 2-ethyl hexanoates, oxides, carbonates, chlorides, dioxides, hydroxides, nitrates, phosphates, sulfates, silicates or mixtures thereof. It is particularly advantageous to utilize a cobalt-based oxidation catalyst. Examples include cobalt carboxylates and sulfonates.
  • the weight ratio of the transition metal-based oxidation catalyst to the magnesium compound, on the basis of the weight of the transition metal and the magnesium is from 50:1 to 1:50.
  • the ratio is from 10:1 to 1:10,5:1 to 1:5, 10:1 to 1:1, 8:1 to 1:1 or 5:1 to 1:1.
  • the magnesium compound is present in an amount of about 5 to about 100 ppm, more specifically about 10 to about 50 ppm, and in particular about 20 to about 40 ppm, on basis of the weight of magnesium in the total composition, and that the transition metal based oxidation catalyst is present in an amount of 30 to 200 ppm, more specifically about 50 to about 150 ppm, and in particular about 75 to about 125 ppm, on basis of the weight of the transition metal in the total composition.
  • the magnesium compound is a salt with a counter ion that is capable of acting as a Bronstedt base in the composition.
  • the magnesium compound may be selected from magnesium carboxylates, in particular C 1 -C 18 -carboxylates or C 8 -C 18 -carboxylates.
  • C 1 -C 18 -carboxylates include acetate, propionate, butanoate, pentanoate and hexanoate, octoate, neodecanoate, palmitate, and stearate salts of magnesium, and mixtures thereof.
  • Examples of C 8 -C 18 -carboxylates include octoate, neodecanoate, palmitate, and stearate, benzoate and naphthenate salts of magnesium, and mixtures thereof.
  • C 8 -C 18 -carboxylates examples include octoate, neodecanoate, laurate, myristate, palmitate and stearate, and naphthenate salts of magnesium, and mixtures thereof.
  • the magnesium compound is magnesium stearate.
  • the magnesium compound may be present in combination with a sodium salt with an anion that is capable of acting as a Bronstedt base in the composition.
  • the sodium salt may be selected from sodium carboxylates, in particular C 1 -C 18 -carboxylates or C 1 -C 4 -carboxylates.
  • Examples of such C 1 -C 18 -carboxylates include acetate, propionate, butanoate, pentanoate, hexanoate, octoate, neodecanoate, laurate, myristate, palmitate, stearate, benzoate and naphthenate salts of sodium, and mixtures thereof.
  • C 1 -C 4 -carboxylates examples include fomate, acetate, propionate, and butanate, and mixtures thereof.
  • the sodium salt is sodium acetate or sodium stearate.
  • the additional presence of said sodium salt may improve the IV of the masterbatch to more closely match that of the polyester base resin. This may reduce the haze in the composition.
  • the polyether segments in the copolyester-ether have a number-average molecular weight of from about 600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol
  • the polyether segment is a linear or branched poly (C 2 -C 6 -alkylene glycol) segment
  • the transition metal-based oxidation catalyst is a cobalt compound
  • the magnesium compound is present in an amount of about 5 to about 100 ppm, on basis of the weight of the magnesium in the total composition
  • the transition metal based oxidation catalyst is present in an amount of about 30 to about 200 ppm, on basis of the weight of the transition metal in the total composition.
  • the polyether segments in the copolyester-ether have a number-average molecular weight of from about 600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol
  • the polyether segment is a linear or branched poly (C 2 -C 6 -alkylene glycol) segment
  • the transition metal-based oxidation catalyst is a cobalt compound
  • the magnesium compound is a magnesium salt with an anion that is capable of acting as a Bronstedt base
  • the magnesium compound is present in an amount of about 5 to about 100 ppm, in particular about 20 to about 40 ppm, on basis of the weight of magnesium in the total composition
  • the transition metal based oxidation catalyst is present in an amount of about 30 to about 200 ppm, specifically about 50 to about 150 ppm, and in particular about 75 to about 125 ppm, on basis of the weight of the transition metal in the total composition.
  • the polyether segments in the copolyester-ether have a number-average molecular weight of from about 600 to about 2500 g/mol, in particular about 800 to about 1600 g/mol
  • the polyether segment is a linear or branched poly (C 2 -C 6 -alkylene glycol) segment
  • the transition metal-based oxidation catalyst is a cobalt compound
  • the magnesium compound is a magnesium C 1 -C 18 -carboxylate
  • the magnesium compound is present in an amount of about 5 to about 100 ppm, in particular about 20 to about 40 ppm, on basis of the weight of magnesium in the total composition
  • the transition metal based oxidation catalyst is present in an amount of about 30 to about 200 ppm, in particular 50 to about 150 ppm, on basis of the weight of the transition metal in the total composition.
  • the polyester is a polyethylene terephthalate (co)polyester
  • the transition metal-based oxidation catalyst is a cobalt catalyst, wherein the oxidation catalyst is present in an amount of 500-15000 ppm, on basis of the weight of cobalt in the total masterbatch, and that a magnesium compound is present, wherein the weight ratio of the cobalt catalyst to the magnesium compound, on basis of the weight of the cobalt and the magnesium, is from 10:1 to 1:10.
  • the magnesium compound is present in amounts of about 125 to about 5000 ppm, in particular about 150 to about 3000 ppm, more specifically about 250 to about 2000 ppm, even more specifically about 250 to about 750 ppm, on basis of the weight of the magnesium in the masterbatch.
  • the polyester is a polyethylene terephthalate (co)polyester
  • the transition metal-based oxidation catalyst is a cobalt catalyst, wherein the oxidation catalyst is present in an amount of 1000-7000 ppm, on basis of the weight of cobalt in the total masterbatch, and that a magnesium C 1 -C 18 -carboxylate, in particular a C 8 -C 18 -carboxylate, is present, wherein the weight ratio of the cobalt catalyst to the magnesium compound, on basis of the weight of the cobalt and the magnesium, is from 10:1 to 1:1.
  • the polyester is a polyethylene terephthalate (co)polyester
  • the transition metal-based oxidation catalyst is a cobalt catalyst, in particular a cobalt C 1 -C 18 -carboxylate, wherein the oxidation catalyst is present in an amount of 1000 - 7000 ppm, on basis of the weight of cobalt in the total masterbatch, that a magnesium C 1 -C 18 -carboxylate, in particular a C 8 -C 18 -carboxylate, is present, wherein the weight ratio of the cobalt catalyst to the magnesium compound, on basis of the weight of the cobalt and the magnesium, is from 10:1 to 1:1, and that a sodium C 1 -C 18 -carboxylate, in particular a C 8 -C 18 -carboxylate, is present, wherein the weight ratio of the sodium salt to the magnesium compound, on basis of the weight of the sodium and the magnesium, is from 3:1
  • the kit-of-parts is packaged for storage.
  • the polyester is a polyethylene terephthalate (co)polyester.
  • the copolyester-ether comprises one or more polyether segments having a number-average molecular weight of from about 200 to about 5000 g/mol and is a linear or branched poly (C 2 -C 6 -alkylene glycol) segment.
  • the transition metal based oxidation catalyst in the first masterbatch is present in an amount of about 500 to about 15000 ppm, in particular about 750 to about 10000 ppm, or about 1000 to about 5000 ppm, on basis of the weight of the transition metal in first masterbatch.
  • the first masterbatch comprises a magnesium compound and that the weight ratio of the transition metal-based oxidation catalyst to the magnesium compound present in the first masterbatch, on basis of the weight of the transition metal and the magnesium, is from about 10:1 to about 1:10, in particular about 5:1 to about 1:1.
  • transition metal-based oxidation catalyst is a cobalt compound that is present in an amount of about 500 to about 15000 ppm, in particular about 750 to about 10000 ppm, more specifically about 1000 to about 6000 ppm, on basis of the weight of cobalt in the first masterbatch, and that the magnesium compound is present in an amount of about 125 to about 5000 ppm, in particular about 150 to about 3000 ppm, more specifically about 250 to about 2000 ppm, even more specifically about 250 to about 750 ppm, on basis of the weight of the magnesium in the first masterbatch.
  • the second masterbatch comprises a hindered amine light stabilizers (HALS). It may be advantageous that the HALS is present in the second masterbatch in an amount of about 200 to about 10,000 ppm, in particular about 500 to about 5000 ppm.
  • HALS hindered amine light stabilizers
  • Embodiments in some aspects of the invention may further comprise an antioxidant, in particular one selected from the group consisting of hindered amine light stabilizers (HALS), hindered phenols, benzophenones, sulfur-based antioxidants, and phosphites.
  • HALS hindered amine light stabilizers
  • hindered phenols hindered phenols
  • benzophenones hindered phenols
  • sulfur-based antioxidants sulfur-based antioxidants
  • phosphites phosphites
  • antioxidants include, but are not limited to 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene (CAS: 1709-70-2), tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4'-diylbisphosphonite (CAS: 38613-77-3) or pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS: 6683-19-8).
  • one or more antioxidants are used in a total amount of about 100 ppm to about 10,000 ppm, more specifically about 200 ppm to about 5,000 ppm or about 300 ppm to about 3,000 ppm, and in particular about 500 ppm to about 2,500 ppm, on basis of the total weight of the antioxidant to the total weight of the composition.
  • Embodiments in some aspects of the invention may further comprise additives selected from the group consisting of dyes, pigments, fillers, branching agents, reheat agents, anti-blocking agents, anti-static agents, biocides, blowing agents, coupling agents, flame retardants, heat stabilizers, impact modifiers, crystallization aids, lubricants, plasticizers, processing aids, buffers, and slip agents.
  • additives selected from the group consisting of dyes, pigments, fillers, branching agents, reheat agents, anti-blocking agents, anti-static agents, biocides, blowing agents, coupling agents, flame retardants, heat stabilizers, impact modifiers, crystallization aids, lubricants, plasticizers, processing aids, buffers, and slip agents.
  • additives selected from the group consisting of dyes, pigments, fillers, branching agents, reheat agents, anti-blocking agents, anti-static agents, biocides, blowing agents, coupling agents, flame retardants, heat stabilizers, impact modifiers
  • ionic compatibilizer can for instance be copolyesters prepared by using ionic monomer units as disclosed in WO 2011/031929 A2 , page 5, incorporated herein by reference.
  • compositions, kit-of-parts and methods may be used for preparing various articles of manufacture.
  • Suitable articles include, but are not limited to, film, sheet, tubing, pipes, fiber, container preforms, blow molded articles such as rigid containers, thermoformed articles, flexible bags and the like and combinations thereof.
  • Typical rigid or semi-rigid articles can be formed from plastic, paper or cardboard cartons or bottles such as juice, milk, soft drink, beer and soup containers, thermoformed trays or cups.
  • the walls of such articles may comprise multiple layers of materials.
  • composition comprising X may consist exclusively of X or may include something additional e.g. X + Y.
  • base polyester base polymer
  • base resin base resin
  • the determination of the intrinsic viscosity was determined on a 0.01 g/mL polymer solution in dichloroacetic acid.
  • the chips were pressed in a hydraulic press (pressure: 400 kN at 115°C for about 1 minute; type: PW40 ® Weber, Remshalden-Grunbach, Germany).
  • 480 to 500 mg polymer, either amorphous chips or pressed chips, were weighed on an analytical balance (Mettler AT 400 ® ) and dichloroacetic acid is added (via Dosimat ® 665 or 776 from Metrohm) in such an amount, that a final polymer concentration of 0.0100 g/mL is reached.
  • the polymer is dissolved under agitation (magnetic stirring bar, thermostat with set point of 65°C; Variomag Thermomodul 40ST ® ) at 55°C (internal temperature) for 2.0 hrs. After complete dissolution of the polymer, the solution is cooled down in an aluminum block for 10 to 15 minutes to 20°C (thermostat with set point of 15°C; Variomag Thermomodul 40ST ® ).
  • the viscosity measurement was performed with the micro Ubbelohode viscometer from Schott (type 53820/II; 0 ⁇ : 0.70 mm) in the Schott AVS 500 ® apparatus.
  • the bath temperature is held at 25.00 ⁇ 0.05°C (Schott Thermostat CK 101 ® ).
  • First the micro Ubbelohde viscometer is purged 4 times with pure dichloroacetic acid then the pure dichloroacetic acid is equilibrated for 2 minutes.
  • the flow time of the pure solvent is measured 3 times.
  • the solvent is drawn off and the viscometer is purged with the polymer solution 4 times.
  • the polymer solution is equilibrated for 2 minutes and then the flow time of this solution is measured 3 times.
  • RV relative viscosity
  • the elemental metal content of the ground polymer samples was measured with an Atom Scan 16 ICP Emission Spectrograph from Spektro. 250 mg of the polymer was dissolved via microwave extraction by adding 2.5 mL sulfuric acid (95-97%) and 1.5 mL nitric acid (65%). The solution was cooled, then 1 mL hydrogen peroxide was added to complete the reaction and the solution was transferred into a 25 mL flask using distilled water. The supernatant liquid was analyzed. Comparison of the atomic emissions from the samples under analysis with those of solutions of known elemental ion concentrations was used to calculate the experimental values of elements retained in the polymer samples.
  • non-invasive oxygen measurement systems e.g., supplied by OxySense ® and PreSens Precision Sensing
  • a fluorescence quenching method for sealed packages were employed. They consist of an optical system with an oxygen sensor spot (e.g. OxyDot ® , which is a metal organic fluorescent dye immobilized in a gas permeable hydrophobic polymer) and a fiber optic reader-pen assembly which contains both a blue LED and photo-detector to measure the fluorescence lifetime characteristics of the oxygen sensor spot (e.g. OxyDot ® ).
  • the oxygen measurement technique is based upon the absorption of light in the blue region of the metal organic fluorescent dye of the oxygen sensor spot (e.g., OxyDot ® ), and fluorescence within the red region of the spectrum.
  • the presence of oxygen quenches the fluorescent light from the dye as well as reducing its lifetime.
  • the oxygen level within a package such as a bottle can be measured by attaching an oxygen sensor spot (e.g., OxyDot ® ) inside the package.
  • the oxygen sensor spot is then illuminated with a pulsed blue light from the LED of the fiber optic reader-pen assembly.
  • the incident blue light is first absorbed by the dot and then a red fluorescence light is emitted.
  • the red light is detected by a photo-detector and the characteristic of the fluorescence lifetime is measured. Different lifetime characteristics indicate different levels of oxygen within the package.
  • a PreSens non-invasive and non-destructive oxygen ingress measurement equipment (Fibox 3-trace meter, fiber optic cable and trace oxygen sensor spots) was used to determine the oxygen permeability of the bottle at room temperature (23°C).
  • the trace oxygen sensor spot was first attached onto the inner side wall of a 500 ml transparent PET bottle.
  • the bottle was then filled with deionized and deoxygenated water containing AgNO 3 up to a headspace of approx. 20 ml, inside a nitrogen circulation glove box where the oxygen level of the water inside the bottle was stabilized at a level well below 50 ppb.
  • These bottles were then stored in a conditioning cabinet (Binder 23°C, 50% relative humidity) and the oxygen ingresses were monitored as a function of time using the PreSens oxygen ingress measurement equipment.
  • an average value was first obtained from about 10 readings taken on the output of the trace oxygen spot for each bottle. This was then repeated for all the 5 bottles so as to achieve an overall averaged value for the oxygen ingress through the formulated cap and the wall of the bottle.
  • Oxygen measurements were made on day 0, 1, 2, 3, 8, 14, 21, 28, 42 and 56, 84, 112, and 140, and the average oxygen ingress was determined and reported as ppb.
  • the barrier copolyester-ether of the present invention was dried for about 24 hours at 110 - 120°C under nitrogen atmosphere
  • the catalyst masterbatch of the present invention was dried for about 24 hours at 80 - 90 °C under nitrogen and blended with the dry base resin, melted and extruded into preforms.
  • the preform was then heated to about 85-120°C and stretch-blown into a 0.5 liter contour bottle at a planar stretch ratio of approx. 8.
  • the stretch ratio is the stretch in the radial direction times the stretch in the length (axial) direction.
  • a preform is blown into a bottle, it may be stretched about two times in the axial direction and stretched up to about four times in the hoop direction giving a planar stretch ratio of up to eight (2x4). Since the bottle size is fixed, different preform sizes can be used for obtaining different stretch ratios.
  • the sidewall thickness of the bottles was > 0.25 mm.
  • Copolyester-ether was prepared using continuous polymerization process: A slurry of terephthalic acid and glycol in a small molar excess of glycol (PTA/EG molar ratio ⁇ 1:1.15) were continuously charged to the primary esterification reactor. The amount of slurry added to the primary esterification reactor was controlled by a flow measuring device. In the primary esterification reactor, terephthalic acid and glycol reacted at 250-260°C and 2-4 bar excess pressure under water elimination. The resulting low molecular weight esterification product was then transferred (via pump) to another reactor (secondary esterifier).
  • a titanium catalyst (Sachtleben Hombifast HS06 ® , 12 ppm Ti based on the final polymer) and 30 wt.-% of poly(tetramethylene oxide) glycol (Terathane ® Polyetherglycol, having a number average molecular weight of 1400 g/mole, stabilized with 200 ppm Ethanox ® 330, CAS: 1709-70-2) based on the final polymer weight were then added to the reaction mixture.
  • the polycondensation, the elimination of glycol under reduced pressure started at 250-260°C.
  • the dwell time of the reaction mixture pre-condensate was again controlled by a flow measuring device.
  • the pre-condensate was then discharged consecutively in two downstream reactors where the dwell time was controlled via the level of the reaction mixture in each reactor.
  • glycol was distilled out of the reaction mixture under increased temperature and reduced pressure until the desired polymerization degree was achieved.
  • the desired polymer melt flowed through the reactor discharge pump into a cooling bath filled with deionized water. After the polymer strand cooled, it was pelletized with a Pell-tec pelletizer.
  • the intrinsic viscosity of the final stabilized copolyester-ether barrier resin was 0.759 dl/g.
  • Example 1b Compounding of copolyester-ether (COPE E1) with a stabilizer
  • Example 1a The copolyester-ether described in Example 1a with an intrinsic viscosity of 0.759 dl/g was used for the compounding trials.
  • the COPE E1 Prior to the extrusion the COPE E1 was dried at 160°C under vacuum for 5 hours to remove residual moisture. The COPE E1 was then mixed with 2000 ppm N,N'-bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendiamine (Uvinul ® 4050, CAS: 124172-53-8) via salt and pepper method and the resulting mixture was subsequently extruded using an intermeshing, co-rotating, twin screw extruder manufactured by Leistritz AG. The process conditions used during the experiment are described below:
  • the molten materials were extruded into a water bath and then pelletized.
  • the intrinsic viscosity of the compounded material is about 0.497 dl/g.
  • Example 2 Synthesis of the catalyst masterbatch: Compounding of the polyethylene terephthalate (co)polyester with the transition metal
  • the commercial Type7090 from Invista Resin &Fibers GmbH with an intrinsic viscosity of 0.86 dl/g was used for the compounding trials. Prior to the extrusion the Type 7090 was dried at 180°C under vacuum for 5 hours to remove residual moisture. Different mixtures of stearates in a define ratio were melted and filled in an addition pump applied at a late dosage unit at the extruder prior the compounding. The Type 7090 was extruded using an intermeshing, co-rotating, twin screw extruder manufactured by Leistritz AG. Thereby the stearate mixtures were added at the late dosage unit to the extruder. The process conditions used during the experiment are described below:
  • the molten materials were extruded into a water bath and then pelletized.
  • the different stearate mixtures as well as some physical properties of the material are summarized in the Table 1 below.
  • the target concentration for cobalt was 2286 ppm.
  • the target concentration for the metal of the metal stearate was 571 ppm.
  • the final concentrations i.e.
  • Example 1a The copolyester-ether of Example 1a and the different catalyst masterbatches as indicated in Table 1 were dried at 80°C under vacuum for 12 hours and blended with the commercial antimony based resin 1101 with an intrinsic viscosity of 0.81 from Invista Resin&Fibers GmbH, Gersthofen, and injection molded into preforms.
  • the preforms were stretch blow molded into 500 mL, 28 g bottles. The oxygen permeation of these bottles was measured and the oxygen uptake is reported in Figure 1 .
  • the use of a magnesium compound substantially decreases the oxygen uptake in comparison to other metals such as zinc, aluminium, calcium, manganese or sodium.
  • the presence of a magnesium compound in the bottle resin composition also allows reducing the amount of cobalt oxidation catalyst required for obtaining satisfying oxygen barrier properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP14179890.0A 2014-08-05 2014-08-05 Verbesserte Polyester-Ether-Harzmischungen Withdrawn EP2982713A1 (de)

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EP14179890.0A EP2982713A1 (de) 2014-08-05 2014-08-05 Verbesserte Polyester-Ether-Harzmischungen
US15/506,547 US10428199B2 (en) 2014-08-05 2015-08-04 Polyester-ether resin blends
PCT/US2015/043595 WO2016022550A1 (en) 2014-08-05 2015-08-04 Improved polyester-ether resin blends
CN201580053387.XA CN107075136B (zh) 2014-08-05 2015-08-04 改进的聚酯-醚树脂共混物

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US20080161465A1 (en) * 2006-12-28 2008-07-03 Jason Christopher Jenkins Oxygen-scavenging polyester compositions useful for packaging
WO2009032560A1 (en) * 2007-08-31 2009-03-12 Invista Technologies S.Ar.L. Oxygen scavenging plastic compositions
WO2010096459A2 (en) 2009-02-20 2010-08-26 Invista Technologies S. Ar.L. Oxygen scavenging resin with short induction period
WO2011031929A2 (en) 2009-09-11 2011-03-17 Invista Technologies S.A.R.L. Method for improved polyester resin blends for oxygen scavenging and products thereof
CN103834150A (zh) * 2014-03-12 2014-06-04 北京崇高纳米科技有限公司 一种用于生产啤酒瓶的材料组合物与该啤酒瓶的生产方法

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CN107075136B (zh) 2019-11-05

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